Deep non-frangible stress profiles and methods of making

ABSTRACT

A non-frangible glass article strengthened by a dual or two-step ion exchange (IOX) process, where the first IOX step leads to a depth of compressive layer FSM_DOL&gt;0.1·t or, in some embodiments, FSM_DOL&gt;0.15·t, where t is the thickness of the glass, is provided. The glass article has a compressive stress CS1 after the first IOX step at the surface of from 100 MPa to 400 MPa or, in some embodiments, from 150 MPa to 300 MPa. The first IOX step is followed by a second IOX step, leading to a “spike” compressive stress CS2 after the second IOX step at the surface of greater than 500 MPa or, in some embodiments, 700 MPa. The width of the spike generated by the second IOX is between 1 μm and 30 μm, or between 8 μm and 15 μm, using the criteria where the magnitude (absolute value) of the slope of the spike is higher than 20 MPa/μm.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application and claims the benefit ofpriority under 35 U.S.C. § 120 of U.S. application Ser. No. 16/296773filed on Mar. 8, 2019, which in turn, is a divisional application andclaims the benefit of priority under 35 U.S.C. § 120 of U.S. applicationSer. No. 14/932411 filed on Nov. 4, 2015, which in turn, claims thebenefit of priority under 35 U.S.C. § 119 of U.S. ProvisionalApplication Ser. No. 62/074872 filed on Nov. 4, 2014, the contents ofeach of which is relied upon and incorporated herein by reference intheir entireties.

BACKGROUND

The disclosure relates to stress profiles in glasses. More particularly,the disclosure relates to glasses having deep compressive stressprofiles. Even more particularly, the disclosure relates to glasseshaving deep compressive stress profiles and exhibiting non-frangiblebehavior.

Chemically strengthened glasses are widely used in displays forhand-held electronic devices such as phones, notebooks and the like.Chemical strengthening creates a compressive layer at the surface of theglass and a tensile region in the central portion of the glass.Compressive stress (CS) and depth of layer (DOL) are typicallydetermined from surface stress measurements (FSM) using commerciallyavailable instruments such as, for example, the FSM-6000, surface stressmeter manufactured by Luceo Co., Ltd. (Tokyo, Japan) or the like.

For strengthened glass articles in which the compressive stress layersextend to deeper depths within the glass, the FSM technique may sufferfrom contrast issues that affect the observed DOL. At deeper DOL values,there may be inadequate contrast between the TE and TM spectra, thusmaking the calculation of the difference between TE and TM spectra—andaccurately determining the DOL—more difficult. Moreover, the FSMsoftware analysis is incapable of determining the compressive stressprofile (i.e., the variation of compressive stress as a function ofdepth within the glass). In addition, the FSM technique is incapable ofdetermining the depth of layer resulting from the ion exchange ofcertain elements such as, for example, ion exchange of sodium forlithium, that are present in the glass.

SUMMARY

The present disclosure extends the range of possible compressive stressprofiles. Modifications to metrology based on the Orihara FSM instrumenthave enabled measurement of are chemically strengthened glasses with“super-deep” depth of compressive layer DOL; i.e., glass samples havinga depth of compressive layer of greater than about 120 μm and, in someembodiments, greater than about 140 μm with standard deviation around 4as determined by surface stress/FSM measurements (referred to herein as“FSM_DOL” or simply “DOL”). In some embodiments, the DOL may be about186 μm with a standard deviation of about 10 μm have been obtained. Theglasses are non-frangible—i.e., the glasses do not exhibit frangible(explosive or energetic fragmentation) behavior upon impact or insult.

Accordingly, in one aspect, a strengthened glass article is provided.The glass article has a thickness t and a compressive layer extendingfrom a surface of the glass article to a depth of layer DOL of greater0.1·t. The glass article has a maximum compressive stress CS of greaterthan about 500 MPa at the surface, a stress profile having a spikeregion in a range from about 1 μm to about 30 μm. The stress profile inthe spike region has a slope. The slope has an absolute value of greaterthan about 20 MPa/μm.

In another aspect, a glass article having a thickness tin a range fromabout 0.2 mm to about 1.5 mm, a compressive layer extending from asurface of the glass article to a depth of layer DOL or depth ofcompression DOC, and a tensile region under a physical center tension CTextending from the depth of layer or depth of compression to the centerof the glass at t/2 is provided. The physical center tension CT isgreater than|−1.956×10^(−16×)t⁶+1.24274×10⁻¹²×t⁵−3.09196×10⁻⁹×t⁴+3.80391×10⁻⁶×t³−2.35207×10⁻³×t²+5.96241×10⁻¹×t+36.5994|,and the glass article has a total elastic energy normalized perthickness of the glass E_(total), wherein (E_(total)/t)=174.75 J/m²·mm.

In yet another aspect, a glass article having a thickness tin a rangefrom about 0.3 mm to about 1 mm, a compressive layer extending from asurface of the glass article to a depth of layer DOL or depth ofcompression DOC, and a tensile region under a physical center tension CTextending from the depth of layer or depth of compression to the centerof the glass at t/2 is provided. The physical center tension CT isgreater than|−1.956×10⁻¹⁶×t⁶+1.24274×10⁻¹²×t⁵−3.09196×10⁻⁹×t⁴+3.80391×10⁻⁶×t³−2.35207×10⁻³×t²+5.96241×10⁻¹×t+36.5994|,and has an elastic energy stored in the interior of the sample intension of E_(interior), wherein (E_(interior)/t)=30 J/m²·mm.

In another aspect, a glass article strengthened by a two-step ionexchange (IOX) process and having a stress profile is provided. Theglass article has a thickness t in a range from about 0.4 mm to about 1mm and a center at t/2, a compressive layer extending from a surface ofthe glass article to a depth of layer DOL or a depth of compression DOC,and a tensile region under a physical center tension CT extending fromthe depth of layer to the center of the glass article. The glass articlehas a compressive stress CS1 after the first ion exchange step at thesurface of from 100 MPa to 400 MPa and, in some embodiments, from 150MPa to 300 MPa, and a depth of layer FSM_DOL greater than 0.1·t or, insome embodiments, greater than 0.15·t following the first ion exchangestep. The first ion exchange step is followed by a second ion exchangestep after which the glass article has a compressive stress CS2 ofgreater than about than 500 MPa or, in some embodiments, greater than700 MPa, at the surface and has a stress profile having a spike regionin a range from about the surface to about 30 μm or, in someembodiments, to about 8 μm-15 μm. The stress profile in the spike regionhas a slope, which has an absolute value of greater than about 20MPa/μm.

A method of strengthening a glass article is also provided. The glassarticle has a thickness t and a center at t/2. The method comprises: ionexchanging the glass article in a first ion exchange bath comprising apotassium salt and at least 30 wt % of a sodium salt to form acompressive layer having a compressive stress CS1 at the surface of fromabout 100 MPa to about 400 MPa, the compressive layer extending from asurface of the glass article to a depth of layer FSM_DOL of greater than0.1·t, or depth of compression DOC, and a tensile region under aphysical center tension CT extending from the depth of layer or depth ofcompression to the center of the glass article; and ion exchanging theglass article in a second ion exchange bath comprising at least 90 wt %of a potassium salt to form a spike region extending from the surface toabout 30 μm below the surface. The spike region has a maximumcompressive stress CS of greater than about 500 MPa at the surface,wherein the stress profile in the spike region has a slope, the slopehaving an absolute value of greater than about 20 MPa/μm.

These and other aspects, advantages, and salient features of the presentdisclosure will become apparent from the following detailed description,the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of typical values of physical center tension (1VIPa)limits as a function of sample thickness;

FIG. 2 is a plot of a stress profile of a double ion exchange sample;

FIG. 3 is a map of the area of interest for an alkali aluminosilicateglass having a Poisson ratio υ=65 GPa and a Young's modulus E=65 GPa;

FIG. 4 is a second map of the area of interest for the case of an alkalialuminosilicate glass which has a Poisson ratio υ=65 GPa and a Young'smodulus E=65 GPa;

FIG. 5 is an example of a compressive stress profile for a non-frangibleglass sample strengthened using a first ion exchange step of 32.1 hoursat a temperature of 460° C. in a bath containing 57 wt % NaNO₃ and 53 wt% KNO₃; and

FIG. 6 is an example of a compressive stress profile for a glass havinga thickness of 500 μm.

DETAILED DESCRIPTION

In the following description, like reference characters designate likeor corresponding parts throughout the several views shown in thefigures. It is also understood that, unless otherwise specified, termssuch as “top,” “bottom,” “outward,” “inward,” and the like are words ofconvenience and are not to be construed as limiting terms. In addition,whenever a group is described as comprising at least one of a group ofelements and combinations thereof, it is understood that the group maycomprise, consist essentially of, or consist of any number of thoseelements recited, either individually or in combination with each other.Similarly, whenever a group is described as consisting of at least oneof a group of elements or combinations thereof, it is understood thatthe group may consist of any number of those elements recited, eitherindividually or in combination with each other. Unless otherwisespecified, a range of values, when recited, includes both the upper andlower limits of the range as well as any ranges therebetween. As usedherein, the indefinite articles “a,” “an,” and the correspondingdefinite article “the” mean “at least one” or “one or more,” unlessotherwise specified. It also is understood that the various featuresdisclosed in the specification and the drawings can be used in any andall combinations.

As used herein, the terms “glass article” and “glass articles” are usedin their broadest sense to include any object made wholly or partly ofglass. Unless otherwise specified, all compositions are expressed interms of mole percent (mol %).

It is noted that the terms “substantially” and “about” may be utilizedherein to represent the inherent degree of uncertainty that may beattributed to any quantitative comparison, value, measurement, or otherrepresentation. These terms are also utilized herein to represent thedegree by which a quantitative representation may vary from a statedreference without resulting in a change in the basic function of thesubject matter at issue. Thus, a glass that is “substantially free ofMgO” is one in which MgO is not actively added or batched into theglass, but may be present in very small amounts as a contaminant—e.g.,less than about 0.1 mol %.

Referring to the drawings in general and to FIG. 1 in particular, itwill be understood that the illustrations are for the purpose ofdescribing particular embodiments and are not intended to limit thedisclosure or appended claims thereto. The drawings are not necessarilyto scale, and certain features and certain views of the drawings may beshown exaggerated in scale or in schematic in the interest of clarityand conciseness.

Described herein are chemically strengthened glasses with “super-deep”DOL; i.e., glass samples having a depth of compressive layer of greaterthan about 120 μm and, in some embodiments, greater than about 140 μm,with a standard deviation around 4 μm, as determined by surfacestress/FSM measurements (referred to herein as “FSM_DOL” or simply“DOL”). In some embodiments, the DOL may be about 186 μm with a standarddeviation of about 10 μm.

The glasses described herein are ion exchangeable alkali aluminosilicateglasses, which, in some embodiments, are formable by down-drawprocesses, such as slot-draw, or fusion-draw processes that are known inthe art. In particular embodiments, such glasses may have a liquidusviscosity of at least about 100 kiloPoise (kP), or at least about 130kP. In one embodiment, the alkali aluminosilicate glass comprises SiO₂,Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein0.75≤[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≤1.2, where M₂O₃=Al₂O₃+B₂O₃.In some embodiments, the alkali aluminosilicate glass comprises orconsists essentially of: from about 40 mol % to about 70 mol % SiO₂;from 0 mol % to about 28 mol % B₂O₃; from 0 mol % to about 28 mol %Al₂O₃; from about 1 mol % to about 14 mol % P₂O₅; and from about 12 mol% to about 16 mol % R₂O and, in certain embodiments, from about 40 toabout 64 mol % SiO₂; from 0 mol % to about 8 mol % B₂O₃; from about 16mol % to about 28 mol % Al₂O₃; from about 2 mol % to about 12 mol %P₂O₅; and from about 12 mol % to about 16 mol % R₂O. In someembodiments, 11 mol %≤M₂O₃≤30 mol %; in some embodiments, 13 mol%≤R_(x)O≤30 mol %, where R_(x)O is the sum of alkali metal oxides,alkaline earth metal oxides, and transition metal monoxides present inthe glass; and in still other embodiments, the glass is lithium-free.These glasses are described in patent application Ser. No. 13/305,271,entitled “Ion Exchangeable Glass with Deep Compressive Layer and HighDamage Threshold,” filed Nov. 28, 2011, by Dana Craig Bookbinder et al.and claiming priority from U.S. provisional patent application No.61/417,941, filed on Nov. 30, 2010, and having the same title, thecontents of which are incorporated herein by reference in theirentirety.

In certain embodiments, the alkali aluminosilicate glass comprises atleast about 4 mol % P₂O₅, wherein (M₂O₃(mol %)/R_(x)O(mol %))<1, whereinM₂O₃=Al₂O₃+B₂O₃, and wherein R_(x)O is the sum of monovalent anddivalent cation oxides present in the alkali aluminosilicate glass. Insome embodiments, the monovalent and divalent cation oxides are selectedfrom the group consisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, MgO, CaO, SrO,BaO, and ZnO. In some embodiments, the glass is lithium-free andconsists essentially of from about 40 mol % to about 70 mol % SiO₂; fromabout 11 mol % to about 25 mol % Al₂O₃; from about 4 mol % to about 15mol % P₂O₅; from about 13 mol % to about 25 mol % Na₂O; from about 13 toabout 30 mol % R_(x)O, where R_(x)O is the sum of the alkali metaloxides, alkaline earth metal oxides, and transition metal monoxidespresent in the glass; from about 11 to about 30 mol % M₂O₃, whereM₂O₃=Al₂O₃+B₂O₃; from 0 mol % to about 1 mol % K₂O; from 0 mol % toabout 4 mol % B₂O₃, and 3 mol % or less of one or more of TiO₂, MnO,Nb₂O₅, MoO₃, Ta₂O₅, WO₃, ZrO₂, Y₂O₃, La₂O₃, HfO₂, CdO, SnO₂, Fe₂O₃,CeO₂, As₂O₃, Sb₂O₃, Cl, and Br; the glass is lithium-free; and1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3, where R₂O is the sum of monovalent_cationoxides present in the glass. The glass is described in U.S. Pat. No.9,156,724 by Timothy M. Gross, entitled “Ion Exchangeable Glass withHigh Crack Initiation Threshold,” filed Nov. 15, 2012, and U.S. Pat. No.8,756,262 by Timothy M. Gross, entitled “Ion Exchangeable Glass withHigh Crack Initiation Threshold,” filed Nov. 15, 2012, both claimingpriority to U.S. Provisional Patent Application No. 61/560,434 filedNov. 16, 2011. The contents of the above patent and applications areincorporated herein by reference in their entirety.

Glass samples with super-deep DOL μm were chemically strengthened in ionexchange baths having different “poisoning” levels—i.e., baths of apotassium salt “poisoned” with a sodium salt), and a number of them werefound not to exhibit frangible behavior (explosive and energeticfragmentation upon impact or insult, often delayed) despite exceedingwhat has been considered to be the center tension CT limit above whichsuch behavior is typically observed, thus confirming that the totalenergy criteria drives frangibility in these cases. Accordingly, theglasses exhibit non-frangible behavior in a regime where such behavioris not expected.

Frangible behavior is characterized by at least one of: breaking of thestrengthened glass article (e.g., a plate or sheet) into multiple smallpieces (e.g., ≤1 mm); the number of fragments formed per unit area ofthe glass article; multiple crack branching from an initial crack in theglass article; violent ejection of at least one fragment to a specifieddistance (e.g., about 5 cm, or about 2 inches) from its originallocation; and combinations of any of the foregoing breaking (size anddensity), cracking, and ejecting behaviors. As used herein, the terms“frangible behavior” and “frangibility” refer to those modes of violentor energetic fragmentation of a strengthened glass article absent anyexternal restraints, such as coatings, adhesive layers, or the like.While coatings, adhesive layers, and the like may be used in conjunctionwith the strengthened glass articles described herein, such externalrestraints are not used in determining the frangibility or frangiblebehavior of the glass articles.

Frangible behavior and non-frangible behavior of strengthened glassarticles may be determined by a point impact test using an instrumentsuch as, for example, a scribe with a tungsten carbide tip, that isdelivered to the surface of the glass article with a force that is justsufficient to release the internally stored energy present within thestrengthened glass article. That is, the point impact force issufficient to create at least one new crack at the surface of thestrengthened glass sheet and extend the crack through the compressivestress CS region (i.e., depth of layer) into the region that is undercentral tension CT.

Accordingly, the chemically strengthened glasses described herein are“non-frangible” —i.e., they do not exhibit frangible behavior asdescribed hereinabove when subjected to impact by a sharp object.

Described herein are chemically strengthened glass articles for whichFSM_DOL>0.1·t and, in some embodiments, FSM_DOL>0.15·t, where t is thethickness of the sample. The glasses are strengthened in an ion exchangebath containing a potassium salt that is “poisoned” with greater thanabout 30 wt % of a sodium salt such as NaNO₃. The thickness t is in arange from about 400 μm (0.4 mm) to about 2000 μm (2 mm).

Samples may also be strengthened using a two-step ion exchange (doubleIOX) process to further increase the compressive stress at the surfaceof the glass and thus create a compressive stress “spike” at the surfaceand extending to a depth of about 30 μm below the surface, and a“super-deep” DOL of about 150 μm without demonstrating frangibility.

Super-deep DOL samples using a double IOX process with a spike and FSMmeasured depth of layer FSM_DOL of greater than 120 μm, in someembodiments, ranging from about 140 μm to about 150 μm, and, in stillother embodiments, possibly reaching FSM_DOL of at least about 186 μmare provided. These double ion-exchanged samples with a spike have acompressive stress maximum at in a range from about 800 MPa to about 900MPa and are not frangible.

Compressive stress CS and depth of layer DOL are measured using thosemeans known in the art. Such means include, but are not limited to,measurement of surface stress (FSM) using commercially availableinstruments such as the FSM-6000, manufactured by Luceo Co., Ltd.(Tokyo, Japan), or the like, and methods of measuring compressive stressand depth of layer are described in ASTM 1422C-99, entitled “StandardSpecification for Chemically Strengthened Flat Glass,” and ASTM1279.19779 “Standard Test Method for Non-Destructive PhotoelasticMeasurement of Edge and Surface Stresses in Annealed, Heat-Strengthened,and Fully-Tempered Flat Glass,” the contents of which are incorporatedherein by reference in their entirety. Surface stress measurements relyupon the accurate measurement of the stress optical coefficient (SOC),which is related to the birefringence of the glass. SOC in turn ismeasured by those methods that are known in the art, such as fiber andfour point bend methods, both of which are described in ASTM standardC770-98 (2008), entitled “Standard Test Method for Measurement of GlassStress-Optical Coefficient,” the contents of which are incorporatedherein by reference in their entirety, and a bulk cylinder method.

As used herein, the terms “DOL” and “FSM_DOL” refer to the depth of thecompressive layer as determined by surface stress measurements.

For strengthened glass articles in which the compressive stress layersextend to deeper depths within the glass, the FSM technique may sufferfrom contrast issues that affect the observed DOL value. At deeperdepths of compressive layer, there may be inadequate contrast betweenthe TE and TM spectra, thus making the calculation of the differencebetween the spectra of bound optical modes for TM and TEpolarization—and accurate determination the DOL—more difficult.Moreover, the FSM software analysis is incapable of determining thecompressive stress profile (i.e., the variation of compressive stress asa function of depth within the glass). In addition, the FSM technique isincapable of determining the depth of layer resulting from the ionexchange of certain elements in the glass such as, for example, the ionexchange of sodium for lithium.

The DOL as determined by the FSM is a relatively good approximation forthe depth of compression (DOC) when the DOL is a small fraction r of thethickness t and the index profile has a depth distribution that isreasonably well approximated with a simple linear truncated profile.When the DOL is a substantial fraction of the thickness, such asDOL≥0.1·t, then the DOC is most often noticeably lower than the DOL. Forexample, in the idealized case of a linear truncated profile, therelationship DOC=DOL·(1−r) holds, where r=DOL/t.

The depth of compression Physical_DOL, also known as IWKB_DOL or DOCL(depth of compression layer) is determined from the spectra of boundoptical modes for TM and TE polarization by using the inverseWentzel-Kramers-Brillouin (IWKB) method. As used herein, Physical_DOLrefers to the depth at which the stress is effectively zero inside theglass. This Physical_DOL is typically less than the FSM_DOL measured bythe FSM instrument for a single Ion exchange process. For double ionexchange processes, the measured FSM_DOL is not a reliable metric, dueto the nature of the instrument and its processing algorithm.

The shape and values of the stress profile in an ion exchanged glass arelimited by a known frangibility limit. This frangibility limit isusually expressed in terms of the center tension CT, which is the valueof the tensile stress in the center of the glass at the position x,where x=thickness/2. The center tension CT naturally occurs due to theforce balance of the stress induced by the sample during the IOXprocess. The integral or sum of the stress at each point in thecompressive part of the profile has to be equal to the integral or sumof the stress at each point in the tensile part of the profile, so thatthe sample is flat and not curved.

If one assumes a single IOX (SIOX) profile, diffusion is guided by aclassical complementary error function. It has been found that thephysical CT varies with glass thickness as shown in FIG. 1.

In FIG. 1, typical values of the physical center tension limit found asa function of the thickness of the sample for a SIOX is shown. A curvecan be fit to the data in FIG. 1 to determine other physical centertension values between thicknesses of 200 μm to 1200 μm. The followingequation may then be used to describe how classical physical CT valuesvary with thickness t, expressed in microns:

CT=−1.956×10⁻¹⁶ ×t ⁶+1.24274×10⁻¹² ×t ⁵−3.09196×10⁻⁹ ×t ⁴+3.80391×10⁻⁶×t ³−2.35207×10⁻³ ×t ²+5.96241×10⁻¹ ×t+36.5994  (1).

When trying to find the ranges of values where a super-deep DOL samplecan be made using a DIOX profile, another important parameter is theconcept of elastic energy. A typical stress profile of a glass samplesubjected to the double ion exchange (DIOX) process is schematicallyshown in FIG. 2. The energy stored in the surface is in compression andthe energy stored in the interior of the sample is tension. The totalenergy E_(total) is the sum of the energy in the surface plus the energyin the interior E_(interior) of the sample. The factor of 2 in theequations shown in FIG. 2 indicates that both sides of the glass must beintegrated and taken into account. The stress profile shown in FIG. 2has a tail due to the first IOX step and a “spike” due to the second IOXstep. The position of the spike occurs where the magnitude (i.e.,absolute value) of the slope of the stress increases to a value ofgreater than about 20 MPa/μm.

The elastic energy stored by the stress profile is calculated accordingto the equation

$\begin{matrix}{{W_{el} = {\frac{\left( {1 - v} \right)}{E}{\int{\sigma^{2}dx}}}},} & (2)\end{matrix}$

where ν is the Poisson ratio (0.22 for the example glass), E is Young'smodulus (about 68 GPa for the example glass), and σ is the stress.

The elastic energy (per unit area of glass) in each compression region(one on each outer surface) is:

$\begin{matrix}{W_{el}^{comp} = {\frac{1 - v}{E}{\int_{0}^{DOC}{\sigma^{2}{{dx}.}}}}} & (3)\end{matrix}$

The elastic energy in the tension region from the compression depth tothe center of the glass substrate is:

$\begin{matrix}{{W_{el}^{tens} = {\frac{1 - v}{E}{\int_{DOC}^{0.5t}{\sigma^{2}dx}}}}.} & (4)\end{matrix}$

The total elastic energy stored in the substrate is twice the sum of theelastic energy of the single compression region and the half tensionregion:

w _(el) ^(tot)=2(W _(el) ^(comp) +W _(el) ^(tens))  (5).

Units for the quantities found in equations 2-5 are:

for stress:

[σ]=MPa≡10⁶N/m²;

for depth: [x]=μm=10⁻⁶m; andfor elastic energy (per unit substrate area):

$\left\lbrack W_{el} \right\rbrack = {{{MPa}^{- 1}*{MPa}*10^{6}\frac{N}{m^{2}}*10^{- 6}m} \equiv \frac{N*m}{m^{2}} \equiv \frac{J}{m^{2}} \equiv {\frac{\mu J}{m\; m^{2}}.}}$

Another metric is the elastic energy per unit substrate area per unitthickness of the substrate, expressed in terms of J/m²mm. This is a moreuniversal parameter because it is independent of the thickness of theglass sample. The elastic energy per thickness of the substrate is validfrom thicknesses ranging from 50 μm to 2000 μm.

In one embodiment, a frangibility criterion may be introduced in theform of a normalized total energy, which defined as:

$\begin{matrix}{{W_{norm}^{tot} = {\frac{w_{el}^{tot}}{\left( \frac{1 - V}{E} \right)} = {\int_{0}^{Thickness}\sigma^{2}}}},} & (6)\end{matrix}$

Based on the above concepts, several double IOX experiments wereperformed on 0.8 mm thick alkali aluminosilicate glass, which isdescribed in U.S. patent application Ser. No. 13/305,271, and has anominal composition of about 57 mol % SiO₂, 0 mol % B₂O₃, about 17 mol %Al₂O₃, about 7% P₂O₅, about 17 mol % Na₂O, about 0.02 mol % K₂O, andabout 3 mol % MgO. Here, detailed stress profile extraction using anIWKB-based algorithm was employed. The method is described in U.S. Pat.No. 9,140,543, entitled “Systems and Methods for Measuring the StressProfile of Ion-Exchanged Glass,” filed May 3, 2012, by Douglas C. Allanet al. and claiming priority from U.S. provisional patent applicationNo. 61/489,800, filed on May 25, 2011, and having the same title, thecontents of which are incorporated herein by reference in theirentirety. The above procedure allowed the approximated physical stressprofile to be extracted and the Physical_DOL or depth of compressionlayer (DOCL) where the stress effectively crosses from compressivestress to tensile stress at—and equals—zero to be pinpointed. Bybalancing tensile and compressive forces across the sample, the physicalCT may be computed. In addition, it is also possible to approximate theelastic energies in compression and tension, as well as the totalelastic energy. In some embodiments, the Physical_DOL is greater than0.8·t and, in some embodiments, greater than 0.12·t.

Examples of super-deep DOL obtained by the double or two-step IOXprocesses are listed in Tables 1a and 1b. Table 1a includes parameters(bath composition, temperature, ion exchange time) for the first andsecond ion exchange baths and compressive stresses CS and depths oflayer DOL, measured by FSM, following each ion exchange step. Table 1blists sample frangibility; depth of compression DOC, compressive stressCS, and physical center tension CT as determined by the IWKB treatment;compressive, tensile, and total energies, and total energy normalizedfor thickness. The glass samples listed in the tables each had athickness of 800 μm and the composition previously describedhereinabove. All samples shown in Tables 1a and b are non-frangible,including some samples for which the physical CT as determined by theIWKB method is above the previously reported CT frangibility limit ofCTmax=−45 MPa for 800 μm thick glass. These samples track the elasticenergy in the sample more closely, and if the correct region of processparameters and stress profile targets of CS and DOL of the first andsecond ion exchange steps are targeted, super-deep depths of layer andcompression that were previously believed to be unattainable may beachieved.

TABLE 1a Ion exchange parameters for the first and second ion exchangebaths and compressive stresses CS and depths of layer DOL, measured byFSM for double-IOX processes (DIOX) for alkali aluminosilicate glasssamples having a thickness of 800 μm. IOX step 1 IOX step 2 Mean MeanMean Mean CS1 DOL1 CS1 DOL1 wt % time Temp (FSM) (FSM) wt % time Temp(FSM) (FSM) Sample Na (h) (° C.) [MPa] [μm] Na (h) (° C.) [MPa] [μm] 157 15 460 201.5 136.6 0.5 0.25 390 201.5 136.6 2 57 17.5 460 196.7 148.70.5 0.25 390 196.7 148.7 3 57 20.1 460 195.8 154.8 0.5 0.25 390 195.8154.8 4 57 26 460 194.2 163.8 0.5 0.25 390 194.2 163.8 5 57 28 460 192.8176.6 0.5 0.25 390 192.8 176.6 6 57 32.1 460 189.1 180.4 0.5 0.25 390189.1 180.4 7 49 15 460 245.5 143.8 0.5 0.25 390 245.5 143.8 8 49 17.25460 242.0 157.0 0.5 0.25 390 242.0 157.0

TABLE 1b Sample frangibility; depth of compression DOC, compressivestress CS, and physical center tension CT as determined by the IWKBtreatment; compressive, tensile, and total energies, and total energynormalized for thickness, determined for the double ion exchangedsamples listed in Table 1a. IWKB IWKB IWKB Compressive Tensile TotalTotal DOC CS CT Energy Energy Energy Energy Sample Frangible (μm) (MPa)(MPa) (J/m²) (J/m²) (J/m²) (J/m² · mm) 1 no 96.81 921.38 −38.73 85.0810.92 96.00 120.00 2 no 100.72 901.46 −40.17 85.47 11.59 97.06 121.33 3no 107.92 927.36 −43.27 87.49 13.12 100.62 125.77 4 no 115.48 983.50−46.46 91.15 14.74 105.89 132.36 5 no 117.53 956.90 −47.36 89.02 15.20104.23 130.28 6 no 124.91 833.79 −50.87 88.14 17.09 105.23 131.54 7 no103.57 948.16 −48.53 105.13 16.75 121.88 152.35 8 no 108.57 882.65−51.09 101.20 18.26 119.47 149.33

The depths of layer DOL1 as measured with the FSM-6000 instrument forthe first ion exchange step were in a range from 136.6 μm to 180.4 μmand the compressive stresses CS1 were in a range from 189 MPa to 245MPa. Following the second IOX step, the CS peak or spike was the rangefrom 852 MPa to 890 MPa. The spike extends from the surface to a depthof about 10 μm to about 11 μm. The peak width may, in practice, besomewhat controlled depending on the immersion time in the second IOXbath. Peak widths from about 1 μm to 25 μm and, in some embodiments, upto about 30 μm are possible for the spike region, depending on theelastic energy stored in the sample.

For glass samples having the above composition with 800 μm thickness,two regions of interest have been identified based on concepts ofphysical CT and elastic energy. The first region of interest is shown inFIG. 3, which is a map of an area of interest for a glass having aPoisson ratio ν=65 GPa and a Young's modulus E=65 GPa. The upper line Ain FIG. 3 is the frangibility limit that has been believed to exist,where CT=−45 MPa for a 800 μm thick sample. Line B in FIG. 3 is thenormalized total energy, which is the integral of the stress squared.Line B is the lower limit with a value of E_(total)=11.65 MPa²·μm×10⁶,and corresponds to a non-normalized total energy of E_(total)=139.8J/m². Normalizing the thickness, (E_(tota)/t)=174.75 J/m²·mm forthickness t=0.8 mm, which is a more universal value that is thicknessindependent. The area of interest is the area between lines A and B andcan be described to be an area where Physical CT>|45 MPa| andE_(total)<139.8 J/m² for a thickness t=800 μm. For a generic thickness,independent physical CT is greater than

|−1.956×10⁻¹⁶ ×t ⁶+1.24274×10⁻¹² ×t ⁵−3.09196×10⁻⁹ ×t ⁴+3.80391×10⁻⁶ ×t³−2.35207×10⁻³ ×t ²+5.96241×10⁻¹ ×t+36.5994|,

where t is the thickness in microns and (E_(total)/t)=174.75 J/m²·mm,where t is the same thickness, expressed in millimeters, for any dualIOX profile. The parameters described by the area between lies A and Bin FIG. 3 describe the poisoning level and ion exchange time of thefirst IOX step. The second region of interest can be visualized with thehelp of FIG. 4, which shows a map of an area of interest for the glassesdescribed herein having a Poisson ratio ν=65 GPa and a Young's modulusE=65 GPa. The upper line C is the frangibility limit that has beenbelieved to exist, where CT=−45 MPa for a 800 μm thick sample. Line D isthe normalized energy stored in the interior E_(interior) of the samplethat is in tension, which is the integral of the stress squared from thepoint where the stress crosses zero to the center of the sample andmultiplied by 2 to take into account both sides of the sample. Line D inFIG. 4 is the lower limit with a value of E_(interior)=2 MPa²·μm×10⁶,which corresponds to a non-normalized total energy of E_(interior)=24J/m². Normalizing the thickness will result in (E_(interior)/t)=30J/m²·mm for a thickness t=800 μm, which is a more universal value thatis independent of thickness. The area of interest to be claimed is thearea between lines C and D can be described as an area where CT isgreater than the equations included in FIG. 1 and (E_(interior)/t)<30J/m²·mm, which is valid for most thicknesses. Alternatively, theparameters describe in the area between lines C and D of FIG. 4 describepoisoning levels and ion exchange times of the first IOX step. This areaagain illustrates the area of interest between limit lines C and black Dand can be described to be an area where: Physical CT>|45 MPa| andE_(interior)<24 J/m² for a thickness t=800 82 m. Alternatively, for ageneric thickness, independent physicalCT>|−1.956×10⁻¹⁶×t⁶+1.24274×10⁻¹²×t⁵−3.09196×10⁻⁹×t⁴+3.80391×10⁻⁶×t³−2.35207×10⁻³×t²+5.96241×10⁻¹×t+36.5994|,where t is the thickness in microns and (E_(interior)/t(mm))=30 J/m²·mmfor any dual or two-step IOX profile.

Additional non-frangible samples having super-deep DOL have also beenobtained using longer IOX times, as shown in FIG. 5, which shows anexample of a super-deep IOX non-frangible stress profile obtained with afirst IOX step of 32.1 hours at a temperature of 460° C. using a bathcontaining 57 wt % of NaNO₃ and the remaining 53 wt % being KNO₃. Thisis followed by second IOX of 15 minutes (0.25 hours) at a temperature of390° C. in a bath containing 0.5 wt % NaNO₃+0.5 wt % of silicic acid+99%KNO₃ to achieve a spike. An inverse-WKB (IWKB) procedure was used toretry the approximated stress profile. An approximate finite-differenceIOX model was also used, resulting in good agreement between theory andmeasurements. The depth of compression layer DOCL where the stresscrosses zero as pointed out by the IWKB and IOX model was about 130 μm.In this case, the values obtained with the FSM-6000 yielded CS=890.3 MPaand DOL=180.4 μm. The range of values between DOL=120 μm and DOL=200 μmand, in some embodiments, between DOL=140 μm to 150 μm, can be deemedsuper-deep DOL samples. This super-deep IOX stress profile again isnon-frangible.

Other examples of super-deep IOX profiles were also obtained at athickness of 500 μm, where a non-frangible stress profile was made aftera first IOX step of 21 hours at 460° C. in a bath containing 60% NaNO₃and 40% KNO₃, resulting in an FSM-6000 DOL in the 146-149 μm range and aCS of 177 MPa. The IWKB procedure was used to characterize the stressprofile with a measured DOCL of 95.8 μm, CT of 60 MPa, Einterior of 10.5J/m² or (E_(interior)/t) of 21 J/m²·m and total energy E_(total) of 30J/m² or (E_(total)/t) of 60 J/m²·mm well below the upper limit of 174.75J/m²·mm. This example is illustrated in FIG. 6. A DIOX stress profile,which includes a spike while maintaining the super-deep DOL as describedin the examples above, may be designed based on this example. Forexample, a DIOX process with a first step ion-exchange at 460° C. usinga NaNO₃/KNO₃ ion exchange bath having a slightly higher level (61 wt %)of NaNO₃ with a duration of 30 hours, combined with the spike processdescribed above, may, for example, be used for 500 μm thick glass toobtain a non-frangible glass having a physical center tension CT of 96.9MPa, total energy (E_(total)/t) of 173.8 J/m²mm, a FSM-6000 DOL of 194μm, DOCL of 91.4 μm, and CS of 823 MPa. In another embodiment of theDIOX process, a first IOX step of 30 hours at 460° C. in a NaNO₃/KNO₃ion exchange bath containing 65 wt % NaNO₃, combined with the spikeprocess described above results in a non-frangible glass having aphysical center tension CT of 85 MPa, a E_(interior)/t of 29.4 J/m²·m, atotal energy E_(tota)/t of 164 J/m²·mm, a FSM-6000 DOL of 194 μm, DOCLof 88.4 μm, and CS of 835 MPa.

In another aspect a method of strengthening a glass article having athickness t is provided. The method comprises a step in which the glassarticle is ion exchanged in a first ion exchange bath comprising apotassium salt and at least 30 wt % of a sodium salt to form acompressive layer extending from a surface of the glass article to adepth of layer FSM_DOL of greater than 0.1·t, or a depth of compressionDOC and a tensile region under a physical center tension CT extendingfrom the depth of layer or depth of compression to the center of theglass at t/2. The compressive layer has a compressive stress CS1 at thesurface from about 100 MPa to about 400 MPa. In a second step, the glassarticle is ion exchanged in a second ion exchange bath comprising atleast 90 wt % of a potassium salt to form a spike region extending fromthe surface to a depth in a range from about 1 μm to about 30 μm belowthe surface. The spike region has a maximum compressive stress CS ofgreater than about 500 MPa at the surface, and the stress profile in thespike region has a slope having an absolute value of greater than about20 MPa/μm. The glass article strengthened according to this method isnon-frangible.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing description should not be deemed to be alimitation on the scope of the disclosure or appended claims.Accordingly, various modifications, adaptations, and alternatives mayoccur to one skilled in the art without departing from the spirit andscope of the present disclosure and appended claims.

1. A glass article having a thickness t, a center at t/2, and acompressive layer extending from a surface of the glass article to adepth of layer DOL of greater 0.1·t, where t is the thickness of theglass, the glass article having a maximum compressive stress CS ofgreater than about 500 MPa at the surface, and a stress profile having aspike region extending from the surface to a depth in a range from 1 μmto about 30 μm below the surface, the stress profile in the spike regionhaving a slope, the slope having an absolute value of greater than about20 MPa/μm; wherein the glass article has a tensile region under aphysical center tension CT extending from the depth of compression tothe center of the glass, wherein the glass article has a total elasticenergy E_(total) and an elastic energy stored in the interior of thesample in tension of E_(interior), wherein (E_(total)/t(mm))<174.75J/m²·mm and (E_(intertor)/t(mm))<30 J/m²·mm.
 2. The glass article ofclaim 1, wherein the compressive layer has a Physical_DOL of greaterthan 0.12·t.
 3. The glass article of claim 2, wherein the maximumcompressive stress CS is greater than about 700 MPa.
 4. The glassarticle of claim 3, wherein the spike region extends from the surface toa depth in a range from about 8 μm to about 15 μm below the surface. 5.The glass article of claim 4, wherein the thickness tin a range fromabout 0.4 mm to about 1 mm, and the physical center tension CT isgreater than |45 MPa|.
 6. The glass article of claim 5, wherein thetotal elastic energy E_(total) is less than about 139.8 J/m².
 7. Theglass article of claim 4, wherein the thickness t in a range from about0.4 mm to about 1 mm, and the physical center tension CT is greater than|63 MPa|.
 8. The glass article of claim 7, wherein the total elasticenergy E_(total) is less than 87.4 J/m².
 9. The glass article of claim1, wherein the depth of layer DOL is greater than about 120 μm, and themaximum compressive stress is greater than about 700 MPa.
 10. The glassarticle of claim 1, wherein the glass article comprises an alkalialuminosilicate glass.
 11. The glass article of claim 10, wherein thealkali aluminosilicate glass comprises at least about 4 mol % P₂O₅ andfrom 0 mol % to about 5 mol % B₂O₃, wherein 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3,where M₂O₃=Al₂O₃+B₂O₃, and R₂O₃ is the sum of monovalent cation oxidespresent in the alkali aluminosilicate glass.
 12. The glass article ofclaim 11, wherein the glass comprises from about 40 mol % to about 70mol % SiO₂; from about 11 mol % to about 25 mol % Al₂O₃; from 0 mol % toabout 5 mol % B₂O₃; from about 4 mol % to about 15 mol % P₂O₅; fromabout 13 mol % to about 25 mol % Na₂O; and from 0 mol % to about 1 mol %K₂O.
 13. The glass article of claim 11, wherein 11 mol %≤M₂O₃≤30 mol %.14. The glass article of claim 11, wherein R_(x)O is the sum of alkalimetal oxides, alkaline earth metal oxides, and transition metalmonoxides present in the glass, and wherein 13 mol %≤R_(x)O≤30 mol %.15. The glass article of claim 10, wherein the glass article islithium-free.
 16. The glass article of claim 1, wherein the physicalcenter tension CT is greater than|−1.956×10⁻¹⁶×t⁶+1.24274×10⁻¹²×t⁵−3.09196×10⁻⁹×t⁴+3.80391×10⁻⁶×t³−2.35207×10⁻³×t²+5.96241×10⁻¹×t+36.5994|,wherein t is in microns.
 17. The glass article of claim 1, wherein theglass is non-frangible.